Oxathiane and oxathiolane derivatives as perfuming agents

ABSTRACT

1,3-Oxathiane and 1,3-oxathiolane derivatives, some which are new, are disclosed as being useful as perfuming and flavoring agents for the preparation of perfumes and perfumed articles and for the manufacture of artificial flavors, flavored foodstuffs, animal feeds, beverages, pharmaceutical preparations and tobacco products.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of our earlier filed andcopending application, Ser. No. 600,275, filed July 31, 1975 and nowabandoned.

SUMMARY OF THE INVENTION

The present invention relates to the use of certain heterocyclicderivatives as flavouring and odoriferous agents. The said compounds,some of which are new, have the formula (I) ##STR1## in which: (a) m andn stand for zero or 1, and each of symbols R¹ and R⁸ represents ahydrogen atom or a saturated or unsaturated, linear or branched alkylradical containing from 1 to 11 carbon atoms, or

(b) n stands for 1 and m represents zero or 1, each of symbols R¹, R²,R³ and R⁴ have the above described meaning, R⁵ and R⁷ each representshydrogen and R⁶ together with R⁸ and the carbon atoms carrying them, inpositions 5 and 6 respectively, form a substituted or unsubstitutedcyclopentane or cyclohexane ring, or

(c) n stands for 1 and m represents zero or 1, each of symbols R¹, R³,R⁵, R⁶ and R⁷ represents hydrogen, R² represents a lower alkyl radicalor a hydrogen atom, R⁴ represents a para-substituted or unsubstitutedphenyl or a substituted or unsubstituted cyclohexenyl radical, and R⁸stands for a lower alkyl, or

(d) n stands for 1 and m represents zero or 1, each of symbols R¹, R³,R⁵, R⁶ and R⁷ represents hydrogen, R² a p-substituted or unsubstitutedphenyl or a substituted or unsubstituted cyclohexenyl radical, R⁴represents a lower alkyl radical or a hydrogen atom, and R⁸ stands for alower alkyl or a hydrogen.

As indicated hereinabove R¹ to R⁸ can represent a saturated orunsaturated, linear or branched alkyl radical. Preferentially, R¹ to R⁸each represents a methyl, ethyl, propyl, butyl, sec-butyl, ter-butyl,pentyl, hexyl, heptyl or octyl radical.

In paragraphs (c) and (d) above it is indicated that R² and R⁸ canrepresent a lower alkyl radical. They preferentially represent a methyl,ethyl or propyl radical.

In the above formula (I) the para-substituted phenyl groups representedby R⁴ or R², as the case may be, include, e.g., p-methyl-phenyl,p-ethyl-phenyl, p-propyl-phenyl, p-methoxy-phenyl and p-ethoxy-phenyl.Preferred para-substituted phenyl groups are p-methyl-phenyl andp-methoxy-phenyl.

R⁴ or R², as the case may be, can also represent a substituted orunsubstituted cyclohexenyl radical. Preferred cyclohexenyl radicals arecyclohex-3-enyl, 2,6,6-trimethyl-cyclohex-2-enyl, and2,6,6-trimethyl-cyclohex-1-enyl. In the event that in formula (I) R⁶together with R⁸ and the carbon atoms carrying them in positions 5 and 6of the heterocyclic ring form a substituted cyclopentane or cyclohexane,the substituent can be, e.g. a lower alkyl radical such as methyl, ethylor propyl. Methyl is a preferred substituent.

The compounds of formula (I) possess interesting organoleptic propertiesand accordingly, are useful as perfuming and odour-modifying agents, andas flavouring and taste-modifying agents. They can be compounded withother odoriferous substances to make perfumery compositions, in themanner conventional in the perfumery art; they can be used combined withcarriers or diluents, for perfuming a wide range of products; they canbe used to modify, enhance or improve the organoleptic properties offoodstuffs, animal feeds, beverages, pharmaceutical preparations andtobacco products, and they can also be used in the manufacture ofartificial flavouring compositions. Accordingly, the present inventionconsists in a composition comprising a compound of formula (I), asdefined above, and a foodstuff, an animal feed, a beverage, apharmaceutical preparation, a tobacco product, another odoriferouscompound, or a perfume base.

This invention relates further to a method for modifying, improving orenhancing the organoleptic properties of foodstuffs, animal feeds,beverages, pharmaceutical preparations and tobacco products; as well asthe odoriferous properties of perfumes and perfumed products, whichmethod comprises adding thereto a small but effective amount of at leastone compound of formula (I).

BACKGROUND OF THE INVENTION

The discovery of the utility of the compounds of formula (I) in thefield of perfumery and flavours is particularly surprising. In theirpure state in fact, these compounds develop a very powerful andunpleasant smell and it is only upon dilution that their odoriferous andflavouring properties become apparent.

The compounds of formula (I) belong to the class of derivatives known as1,3-oxathianes (n=1) and 1,3-oxthiolanes (n=0). Their use, as well asthat of their corresponding oxides (m=1), was hitherto unknown inperfumery and in the flavour art.

We have discovered 2-methyl-4-n-propyl-1,3-oxathiane and itscorresponding oxide, viz. 2-methyl-4-n-propyl-1,3-oxathiane-3-oxide, ascompounds of natural origin which can be isolated from an essential oilobtainable from the juice of the passion-fruit, Passiflora edulisflavicarpa. Passion-fruit juice is a commercial material available, forexample, for Nationwide of Chicago, Food Brokers, Inc., 1400 WinstonPlaza, Melrose Park, Illinois, United States of America.

However, the procedure for isolating the said compounds from naturalpassion-fruit juice is extremely complex and uneconomical. The yield ofessential oil obtained is not higher than 0.0012% by weight of the totaljuice treated. In order to isolate the above mentioned compounds, thejuice is subjected to a preliminary distillation, by means of a specialtechnique known as "thin layer distillation"--vide Helv. Chim. Acta, 45,2186 (1962). This operation yields 18% by weight of an aqueousdistillate from which the desired essential oil can be obtained byextraction with ethyl chloride followed by evaporation of the volatilecomponents. The oil is then separated by column chromatography onsilicic acid, by the procedure described in J. Chromatography 34, 174(1968); and the polar fractions are then subjected to repeatedseparations by preparative gas chromatography to isolate the pureoxathiane derivatives.

Analytical and synthetic studies confirmed that these products werecompounds of previously unknown structure.

The disadvantages and difficulties inherent in the isolation of2-methyl-4-n-propyl-1,3-oxathiane and2-methyl-4-n-propyl-1,3-oxathiane-3-oxide from the essential oilobtained from passion-fruit have been overcome by the discovery of aprocess for preparing synthetically these and the other compounds offormula (I). A particularly valuable feature of the synthetic process isthat it readily yields the pure compounds, which have powerfulorganoleptic characteristics that are stable and perfectly reproducible;wheras, in contradistinction, the properties of the natural essentialoil vary with the origin of the fruit from which it has been extracted,the method of extraction, and the purity of the essential oil recovered.Consequently, the synthetic compounds are useful as flavouring andperfuming ingredients over a wide field of application than the naturalessential oil.

2-Isopropyl-1,3-oxathiolane and its phenyl analogue have been describedby Kipnis et al. J. Am. Chem. Soc., 71, 3555 (1949) as liquids withfresh, aromatic aromas. In actual experience the compounds of theinvention possess organoleptic properties which are far more superiorthan those described by Kipnis. The following Tables show the results offlavour evaluations carried out on 2-methyl-4-propyl-1,3-oxathiane bycomparison with 2-isopropyl-1,3-oxathiolane and2-phenyl-1,3-oxathiolane.

    ______________________________________                                        Evaluation in water                                                           Ingredient     Level    Evaluation                                            ______________________________________                                        1.  2-Methyl-4-    0.1  ppm Sweet, green, fruity                                  propyl-1,3-             typical Passion-fruit                                 oxathiane                                                                     (-00%)                                                                         ##STR2##      0.10 ppm Strong alliaceous note, Cabbage, gas, burnt.                                  Rotten egg.                                            ##STR3##      0.20 ppm Weaker than 1, less fruity Woody, floral                                      Slight egg character                              ______________________________________                                    

    ______________________________________                                        Evaluation in acidified sugar syrup                                           Ingredient     Level    Evaluation                                            ______________________________________                                        1.  2-Methyl-4-    0.10 ppm Fruity, juicy.                                        propyl-1,3-             Typical Passion-fruit.                                oxathiane               Blackcurrant.                                         (100%)                                                                         ##STR4##      0.10 ppm Lacks fruit juicy character. Burnt, gas top                                   note. Alliaceous.                                      ##STR5##      0.20 ppm Less fruity than 1. Woody, floral. Vegetable                                  character.                                        ______________________________________                                         *10 g of a 50% aqueous solution of citric acid in a syrup containing 600      of sucrose per liter water.                                              

    ______________________________________                                        As reinforcer for natural Passion-fruit                                       Juice - Comparison made with unflavoured                                      juice.                                                                        Ingredient     Level    Evaluation                                            ______________________________________                                        1.  2-Methyl-4-    0.10 ppm Enhanced juicy character.                             propyl-1,3-             Fresher top note.                                     oxathiane               Typical.                                              (100%)                                                                         ##STR6##      0.10 ppm Burnt, alliaceous, Coffee. Not recognisable.                                  Direction Durian.                                      ##STR7##      0.20 ppm Green vegetable character. Cooked, fatty. Not                                 typical.                                          ______________________________________                                    

Concerning its olfactive properties, 2-methyl-4-propyl-1,3-oxathiane isclearly distinguishable from the above cited oxathiolane derivativesdescribed by Kipnis. 2-Isopropyl-1,3-oxathiolane possesses an extremelypowerful almost unbearable smell in its pure state. Upon dilution thesame compound developed a strong odour reminiscent of rotten grass andsewage with a "carbide" by-note. 2-Phenyl-1,3-oxathiolane showed aslight spicy-green character and a vague odour reminiscent of bitteralmonds with a slight rotten smell. On the contrary,2-methyl-4-propyl-1,3-oxathiane develops in a 1% by weight solution indiethyl-phthalate a pleasant scent having a fruity-green and freshcharacter reminiscent of the odour developed by black-currant shrubsleaves

Several oxathiane and oxathiolane derivatives have been reported in thepast in the scientific literature. 2-(3-Heptyl)-1,3-oxathiolane and2-(3-amyl)-1,3-oxathiolane have been described in U.S. Pat. No.3,025,214. Pasto et al. [J. Am. Chem. Soc., 89, 4368 (1967)] haveprepared various 1,3-oxathianes which may be alkylated in the2-position. Van Acker et al. [Tetrahedron Letters 1974, 225-8] andStevenson [J. Am. Chem. Soc., 96, 1067 (1974)] have described1,3-oxathiane-5-oxides and 2-t-butyl-1,3-oxathiolanes, respectively.Djerassi et al. [J. Am. Chem. Soc., 75, 3704 (1953)], Rondestvedt [J.Org. Chem. 26, 2247 (1961], De Wolf et al. [Tetrahedron Letters, 1970551-4], Phihlaja et al. [Acta Chem. Scand. 1970, [24], 2257] and Pasanenet al. [Acta Chem. Scand. 1971, [25] 1908] showed a variety of1,3-oxathianes which may be substituted in the 2-and the 6-positions.

None of the above cited references describes or even suggests thepossibility of using the oxathiane or oxathiolane derivatives of thepresent invention as flavour or perfume ingredients and, what is more,no mention appears therein of the organoleptic properties of thedescribed compounds, most of the cited authors having in fact limitedtheir investigations to pure theoretical physico-chemical studies.

PREFERRED EMBODIMENTS OF THE INVENTION

Specific examples of the compounds defined by structural formula (I)include the following:

1. 1,3-oxathiolane

2. 2-methyl-1,3-oxathiolane

3. 5-methyl-1,3-oxathiolane

4. 2,2-dimethyl-1,3-oxathiolane

5. 2,4-dimethyl-1,4-dimethyl-1,3-oxathiolane

6. 2,5-dimethyl-1,3-oxathiolane

7. 2,2,4-trimethyl-1,3-oxathiolane

8. 2-pentyl-1,3-oxathiolane

9. 2-pentyl-5-methyl-1,3-oxathiolane

10. 1,3-oxathiane

11. 2-methyl-1,3-oxathiane

12. 2,2-dimethyl-1,3-oxathiane

13. 4,4,6-trimethyl-1,3-oxathiane

14. 2,4,4,6-tetramethyl-1,3-oxathiane

15. 2-ethyl-4,4,6-trimethyl-1,3-oxathiane

16. 2-propyl-4,4,6-trimethyl-1,3-oxathiane

17. 4-propyl-1,3-oxathiane

18. 2-methyl-4-propyl-1,3-oxathiane

19. 2,2-dimethyl-4-propyl-1,3-oxathiane

20. 2-methyl-2-ethyl-4-propyl-1,3-oxathiane

21. 2-methyl-2,4-dipropyl-1,3-oxathiane

22. 2-ethyl-4-propyl-1,3-oxathiane

23. 2-ter-butyl-4-propyl-1,3-oxathiane

24. 2-pentyl-4-propyl-1,3-oxathiane

25. 2-(pent-1-enyl)-4-propyl-1,3-oxathiane

26. 2-methyl-2-hexyl-4-propyl-1,3-oxathiane

27. 2-octyl-4-propyl-1,3-oxathiane

28. 2-undecyl-4-propyl-1,3-oxathiane

29. 2-methyl-4-heptyl-1,3-oxathiane

30. 2,2-dimethyl-4-heptyl-1,3-oxathiane

31. 2-ethyl-4-heptyl-1,3-oxathiane

32. 2-pentyl-4-heptyl-1,3-oxathiane

32b. 2-methyl-6-propyl-1,3-oxathiane

32c. 2,4,4,6-tetramethyl-2-propyl-1,3-oxathiane

33. 4-(cyclohex-3-en-1-yl)-6-methyl-1,3-oxathiane

34. 2,6-dimethyl-1,4-(cyclohex-3-en-1-yl)-1,3-oxathiane

35. 4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-6-methyl-1,3-oxathiane

36. 2,6-dimethyl-4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-1,3-oxathiane

37. 2,6-dimethyl-4-(2,2,6-trimethyl-cyclohex-6-en-1-yl)-1,3-oxathiane

38. 4-(2,2,6-trimethyl-cyclohex-6-en-1-yl)-6-methyl-1,3-oxathiane

39. 2-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-4-methyl-1,3-oxathiane

40. 4-phenyl-6-methyl-1,3-oxathiane

41. 4-(p-methyl-phenyl)-6-methyl-1,3-oxathiane

42. 2,6-dimethyl-4-(p-methyl-phenyl)-1,3-oxathiane

43. 4-(p-methoxy-phenyl)-6-methyl-1,3-oxathiane

44. 2,6-dimethyl-4-(p-methoxy-phenyl)-1,3-oxathiane

45. 5-butyl-2-oxo-4-thiabicyclo[4.3.0]nonane

46. 3-methyl-5-butyl-2-oxa-4-thiabicyclo[4.3.0]nonane

47. 5,5,9-trimethyl-2-oxa-4-thiabicyclo[4.4.0]decane

48. 2,5,5,9-tetramethyl-2-oxa-4-thiabicyclo[4.4.0]decane

49. 5,5,9-trimethyl-3-ethyl-2-oxa-4-thiabicyclo[4.4.0]decane

50. 5,5,9-trimethyl-3-propyl-2-oxa-4-thiabicyclo[4.4.0]decane

51. 3,5,5,9-tetramethyl-3-propyl-2-oxa-4-thiabicyclo[4.4.0]decane

52. 1,3-oxathiane-3-oxide

53. 2-methyl-1,3-oxathiane-3-oxide

54. 2,2-dimethyl-1,3-oxathiane-3-oxide

55. 4-propyl-1,3-oxathane-3-oxide

56. 2-methyl-4-propyl-1,3-oxathiane-3-oxide

57. 2-pentyl-4-propyl-1,3-oxathiane-3-oxide

58. 2,2diethyl-4-n-propyl-1,3-oxathiane.

In the following Table the above compounds are listed together withtheir physical properties. Whenever a compound is commercially availableor has been previously described in the chemical literature, it will beidentified by the abbreviations "c.a." (commercially available) or"p.k." (prior known), respectively. The temperatures are given indegrees centigrade and the abbreviations have the sens common in theart.

In the herein above given list of compounds whenever mention has beenmade of the alkyl substituents such as, e.g., "propyl" it is deemed torefer to the unbranched radical such as, e.g. "n-propyl".

                                      TABLE                                       __________________________________________________________________________    Product No.                                                                           Physical properties                                                   __________________________________________________________________________    1.         p.k. Suomi Kemistilehti B (1970) 43, 143                           2.         p.k. Suomi Kemistilehti B (1970) 43, 143                           3.     MS: M.sup.+  = 104 (96); m/e: 89 (1), 74 )65), 60 (100), 41                       (99)                                                                      NMR:                                                                              1.4 (3H, d), 2.53 (1H, d/d), 3.08 (1H, d/d), 4.02                             (1H, m), 4.85 (2H, m) δ ppm                                         IR: 2970, 2930, 2860, 2640, 1055, 720 cm.sup.-1                        4.     p.k. Synth. Commun. 4, 6 (1974)                                        5.     MS: M.sup.+  = 118 (53); m/e: 103 (22), 85 (0.5), 74 (100),                       59 (48), 41 (89)                                                          NMR:                                                                              1.35 (3H, d), 1.58 (3H, d), 3.0-4.5 (3H, m), 5.25                             (1H, m) δ ppm                                                6.     p.k. Tetrahedron 28, 3943 (1972)                                       7.     MS: M.sup.+  = 132 (24); m/e: 117 (3), 99 (0.5), 88 (1), 74                       (100), 59 (25), 43 (50), 41 (70)                                          NMR:                                                                              1.39 (3H, d), 1.62 (3H, s), 1.67 (3H, s), 2.76 (1H,                           (d/d), 3.14 (1H, d/d), 4.36 (1H, m) δ ppm                           IR: 2970, 2920, 2860, 2630, 1090, 590 cm.sup.-1                        8.     MS: M.sup.+  = 160 (7); m/e: 89 (100), 60 (48), 61 (45), 45                       (9)                                                                       NMR:                                                                              0.88 (3H, t), 3.0 (2H, d/d), 3.76 (1H, d/d/d), 4.35                           1H, d/t), 5.08 (1H, t) δ ppm                                        IR: 2955, 2925, 2855, 2720, 1070, 658 cm.sup.-1                        9.     MS: M.sup.+ = 174 (8.5); m/e: 127 (2), 115 ( ), 103 (100),                        83 (2), 74 (72), 55 (64), 41 (62).                                        NMR:                                                                              0.90 (3H, t), 1.40 (3H, d), 2.61 (1H, d/d), 3.09                              (1H, d/d), 4.18 (1H, m), 5.15 (1H, t) δ ppm                         IR: 2950, 2915, 2850, 2620, 1090, 655 cm.sup.-1                        10.        p.k. Acta Chem. Scand. 24, 2257 (1970)                             11.        p.k. Acta Chem. Scand. 24, 2257 (1970)                             12.        p.k. Acta Chem. Scand. 24, 2257 (1970)                             13.        B.p. 61°/11 Torr                                                   MS: M.sup.+ = 146 (62), 131 (7.6), 113 (0.9), 102 (20.5), 87                      35.3), 83 (16.1), 74 (31.7), 69 (10.7), 67 (7.6), 59                          (48.7), 56 (61.2), 43 (100), 41 (50.4)                                    NMR:                                                                              (60 MHz; CDCl.sub.3): 1.12-1.63 (5H, m), 1.26 (6H, s),                        3.40-3.92 (1H, sext.), 4.63-5.10 (2H, d of d) δ ppm          14.        B.p. 65°/15 Torr                                                   MS: M.sup.+ = 160 (45.8), 145 (29.5), 132 (1.0), 116 (18.9),                      101 (41.5), 88 (12.1), 83 (42.1), 74 (72.1), 69                               (10.5), 67 (9.7), 61 (53.7), 60 (100), 59 (69.4), 55                          (34.2), 43 (32.1), 41 (45.8)                                              NMR (60 MHz; CDCl.sub.3): 1.23 (6H, s); 1.15-1.55 (8H, m),                        3.47-4.06 (1H, sext.), 4.78-5.15 (1H, q) δ ppm               15.        B.p. 77°/13 Torr                                                   MS: M.sup.+ = 174 (19.8), 145 (100), 116 (3.4), 101 (29.7),                       83 (84.5), 74 (80.7), 69 (12.6), 67 (8.2), 61 (42.5),                         60 (62.3), 59 (63.8), 55 (37.2), 43 (22.7), 41 (58.4)                     NMR (60 MHz; CDCl.sub.3): 0.85-1.10 (3H, t), 1.25 (6H, s),                        1.12-1.95 (7H, m), 3.42-4.02 (1H, sext.), 4.67-4.87                           (1H, t) δ ppm                                                16.        B.p. 95°/13 Torr                                                   MS: M.sup.+ = 188 (13.2), 145 (100), 116 (3.9), 101 (27.8),                       88 (12.8), 83 (76.7), 74 (50.7), 69 (11.4), 67 (6.4),                         61 (39.7), 60 (58.4), 59 (40.2), 55 (44.3), 43                                (13.2), 41 (41.5)                                                         NMR (60 MHz; CDCl.sub.3): 0.8-1.05 (3H, t), 1.25 (6H, s),                         1.15-1.90 (9H, m), 3.40-4.02 (1H, sext.), 4.70-4.97                           (1H, t) δ ppm                                                17.    MS: M.sup.+ = 146 (50); m/e: 114 (27), 103 (95), 73 (100),                        55 (57), 45 (49)                                                          NMR:                                                                              0.92 (3H, t),  1.80 (2H, d/d), 3.02                                           (1H, bm), 3.52 (1H, m), 4.15 (1H, d/tr), 4.80 (2H,                            s) δ ppm                                                            IR: 2950, 2920, 2860, 2720, 1085, 575 cm.sup.-1                        18.        vide p. 28 & 29 of this specification                              19.    MS: M.sup.+ = 174 (37); m/e: 159 (35), 116 (49), 101 (70),                        87 (100), 73 (55), (98), 41 (76)                                          NMR:                                                                              0.90 (3H, tr), 1.47 (3H, s), 1.64 (3H, s), 3.12                               (1H, bm), 3.87 (2H, d/d) δ ppm                                      IR: 2960, 2925, 2870, 2720, 1080, 600 cm.sup.-1                        20.    MS: M.sup.+ = 188 (3.5); m/e: 173 (6), 159 (100), 116 (19),                       101 (41), 83 (66), 73 (57), 55 (87), 43 (75)                              NMR:                                                                              0.95 (6H, m), 1.4 (6H, m), 1.6 (3H, s), 3.09 (1H,                             bm), 4.85 (2H, m) δ ppm                                             IR: 2960, 2920, 2865, 2720, 1080, 585 cm.sup.-1                        22.    MS: M.sup.+ = 174 (13); m/e: 145 (100), 101 (8.5), 83 (24),                       73 (21), 55 (48), 41 (32)                                                 NMR:                                                                              0.99 (6H, m),  2.99 (1H, bm), 3.65 (1H,                                       m), 4.22 (1H, d/tr), 4.64 (1H, tr) δ ppm                            IR: 2960, 2920, 2870, 2840, 2730, 1100, 1075, 575 cm.sup.-1            23.    MS: M.sup.+  = 202 (2); m/e: 146 (100), 83 (27), 73 (5), 55                       (35), 41 (20)                                                             NMR:                                                                              1.0 (12H, bs), 1.4-1.9 (6H, m), 2.98 (1H, bm), 3.65                           (1H, m), 4.25 (1H, d/tr), 4.45 (1H, s) δ ppm                        IR: 2950, 2920, 2855, 2720, 1085, 640 cm.sup.-1                        24.    MS: M.sup.+ = 216 (4); m/e: 145 (100), 117 (3), 101 (8),                          83-  (28), 73 (13), 55 (42), 41 (26)                                      NMR:                                                                              0.89 (6H, bm), 3.0 (1b, bm), 3.62 (1H, m), 4.2 (1H,                           d/t), 4.7 (1H, t) δ ppm                                             IR: 2955, 2920, 2850, 2725, 1085, 660 cm.sup.-1                        25.    MS: M.sup.+ = 214 (31); m/e: 185 (6), 171 (18.5), 145 (5.5),                      131 (2), 116 (22), 98 (60), 87 (70), 73 (47), 55                              (100), 41 (88).                                                           IR: 3040, 3015, 2960, 2880, 1665, 1075, 960                                       720 cm.sup.-1                                                      26.    MS: M.sup.+ = 244 (0.5); m/e: 229 (1), 159 (42), 128 (4), 116                     23.5), 101 (20), 87 (32), 73 (20), 58 (65), 43 (100),                         41 (46)                                                                   NMR:                                                                              0.9 (6H, bm), 1.6 (3H, s), 3.16 (1H, bm), 3.89 (2H,                           m) δ ppm                                                            IR: 2940, 2910, 2850, 2720, 1085, 600 cm.sup.-1                        27.    MS: M.sup.+  = 258 (2); m/e: 145(100), 124 (2.5), 117 (4), 101                    (5), 87 (11), 83 (25), 69 (9.5), 55 (39), 41 (29),                            29 (92)                                                                   NMR:                                                                              0.89 (6H, bm), 2.98 (1H, bm), 3.63 (1H, m), 4.2 (1H,                          d, t), 4.7 (1H, t) δ ppm                                            IR: 2950, 2915, 2845, 2720, 1085, 660 cm.sup.-1                        28.    MS: M.sup.+ = 300 (--); m/e: 166 (2), 145 (100), 116 (5.5),                       101 (5.5), 83 (22), 69 (8.5), 55 (35), 41 (25)                            NMR:                                                                              0.91 (6H, bm), 2.97 (1H, bm), 3.7 (1H, m), 4.19 (1H,                          d/t), 4.69 (1H, t) δ ppm                                            IR: 2940, 2910, 2835, 2720, 1095, 1075, 660 cm.sup.-1                  29.    MS: M.sup.+ = 216 (43): m/e: 201 (57), 170 (78), 157 (2.5),                       143 (37), 129 (18), 115 (61), 101 (54), 87 (85), 73                           (65), 55 (100), 41 (80)                                                   NMR:                                                                              0.89 (3H, t), 1.48 (3H, d), 1.7 (2H, m), 3.01 (1H,                            bm), 3.56 (1H, m), 4.2 (1H, d/t), 4.81 (1H, q) δ ppm                IR: 2950, 2920, 2850, 2720, 1095, 670 cm.sup.-1                        30.    MS: M.sup.+ = 230 (4); m/e: 215 (8), 199(--), 187 (0.5),                          172 (14), 157 (--), 143 (36), 129 (21), 115 (53),                             101 (47), 87 (87), 64 (45), 55 (80), 43 (100)                             NMR:                                                                              0.90 (3H, t), 1.52 (3H, s), 1.69 (3H, s), 3.12 (1H,                           bm), 3.92 (2H, m) δ ppm                                             IR: 2950, 2920, 2850, 2720, 1080, 595 cm.sup.-1                        31.    MS: M.sup.+ = 230 (6.5); m/e 216, (--), 201 (100), 185                            (0.5), 170 (3), 157 (0.5), 143 (2), 129 (1), 115                              (6.5), 97 (13), 83 (33), 69 (33), 55 (48), 41 (42)                        NMR:                                                                              0.99 (6H, m), 2.95 (1H, bm), 3.60 (1H, m), 4.18                               (1H, d/d), 4.61 (1H, t) δ ppm                                       IR: 2955, 2920, 2850, 2725, 1105, 1090, 720 cm.sup.-1                  32.    MS: M.sup.+ = 272 (2); m/e: 201 (100), 182 (0.5), 170 (3),                        157 (0.5), 143 (5.5), 129 (4), 115 (11), 97 (11),                             83 (33), 69 (31), 55 (55), 41 (52)                                        NMR:                                                                              0.87 (6H, bt), 2.97 (1H, bm), 3.6 (1H, m), 4.16                               (1H, d/tr), 4.65 (1H, t) δ ppm                                      IR: 2950, 2920, 2850, 2720, 1090, 720 cm.sup.-1                        32b.       B.p. 75°/9 Torr                                                    NMR:                                                                              0.92 (34.6), 1.46 (3H, d, J=6Hz), 1.2-1.9 (6H, m),                            2.5-3.2 (1H, m), 3.2-3.7 (1H, m), 4.89 (1H, q, J=                             6Hz) δ pm                                                           MS: M.sup.+ = 160 (34), 87 (100), 41 (51), 60 (43), 67 (38),                      80 (36.5), 55 (35.5), 45 (33), 101 (21.5), 116 (21)                32c.       B.p. 89°/11 Torr                                                   MS: 202 (1.7), 187 (3.3), 159 (77.6), 116 (36.0), 101                             (54.2), 87 (22.9), 83 (72.0), 74 (80.4), 69 (20.6),                           67 (10.3), 61 (66.8), 60 (94.4), 59 (64.9), 55                                (38.3), 43 (100), 41 (26.2)                                               NMR (90 MHz; CDCl.sub.3) 0.80-1.06 (3H, t), 1.25 (6H, s),                         1.15-1.90 (12H, m), 3.70-4.25 (1H, m) δ ppm                  33.        B.p. 73°/0.001 Torr                                                MS: M.sup.+ = 198 (10.5), 117 (100), 73 (81), 79 (50), 93                         (34), 45 (31.5), 41 (26.5), 87 (23), 53 (14), 67 (12),                    NMR:                                                                              1.2 (3H, d, J=6Hz), 1.4-2.4 (9H, m), 2.5-4.0 (2H, m),                         4.87 (2H, s), 5.7 (2H, bs) δ ppm                             34.        B.p. 78°/0.001 Torr                                                MS: M.sup.+ = 212 (14), 79 (100), 93 (92), 80 (84), 87 (80),                      131 (76), 92 (66), 91 (55), 45 (52), 41 (47)                              NMR:                                                                              1.16 (1H, d), 1.22 (2H, d), 1.39 (1H, d), 1.46 (2H,                           d), 1.6-2.5 (9H, m), 2.7-4.0 (2H, m), 4.7-5.3 (1H,                            m), 5.7 (2H, s) δ ppm                                        35.        Isomer A - B.p. 100°/0.5 Torr                                      MS: M.sup.+ = 240 (3.5), 73 (100), 117 (61), 87 (12), 41 (12),                    55 (5.7)                                                                  NMR:                                                                              0.88 (3H, s), 1.08 (3H, s), 1.3 (3H, d, J=6Hz), 1.82                          (3H, m), 3.55 (1H, m), 4.25 (1H, bm), 4.54 (1H, d,                            J=11Hz), 5.19 (1H, d, J=11Hz), 5.45 (1H, m) δ ppm                       Isomer B - B.p. 100°/0.5 Torr                                      MS: M.sup.+ = 240 (4), 73 (100), 117 (65), 41 (10.7), 87                          (10.4), 55 (5.5)                                                          NMR:                                                                              0.9 (3H, s), 1.09 (3H, s), 1.18 (3H, d, J=6Hz), 1.8                           3H, m), 3.1-3.8 (2H, m), 4.87 (2H, s), 5.5 (1H, m)                            δ ppm                                                        36.        B.P. 100°/0,5 Torr                                                 MS: M.sup.+ =  254 (2), 87 (100), 131 (34), 45 (10), 41 (9),                      123 (4.6), 107 (4.4), 55 (4.1)                                            NMR:                                                                              0.88 (3H, s), 1.07 (3H, s), 1.2 (3H, d, J=6Hz),                               1.45 (3H, d, J=6Hz), 1.8 (3H, m) 3.1-3.8 (2H, m),                             4.85 (1H, q, J=6Hz) δ ppm                                    37.        B.p. 85°/0.05 Torr                                                 MS: M.sup.+ = 254 (35), 41 (100), 135 (85), 107 (76), 43 (71),                    55 (71), 61 (71), 93 (69), 161 (67), 91 (62), 119                             (62), 121 (62), 69 (59), 167 (59), 79 (47)                                NMR:                                                                              0.99 (3H, s), 1.09 (3H, s), 1.24 (3H, d, J=6Hz),                              1.45 and 1.5 (3H, d, d, J=6Hz), 1.88 (3H, s), 3.3--                           4.2 (2H, m), 4.6-5.4 (1H, m) δ ppm                           38.        Isomer A - B.p. 95°/0.2 Torr                                       MS: M.sup.+ = 240 (45.5), 135 (100), 43 (93), 91 (82), 149                        (75), 41 (72), 93 (70), 107 (61), 45 (47.5), 55                               (46.5), 69 (43), 79 (41), 81 (38.5), 121 (37.5)                           NMR:                                                                              1.0 (3H, s), 1.09 (3H, s), 1.2 (3H, d, J=6Hz), 1.88                           (3H, s), 3.3-3.8 (2H, m), 4.87 (2H, s) δ ppm                 38.        Isomer B - B.p. 95°/0.2 Torr                                       MS: M.sup.+ = 240 (33), 43 (100), 135 (98), 93 (80), 41 (77),                     95 (69), 149 (65), 107 (64), 121 (51), 55 (49), 69                            (43.5), 79 (42)                                                           NMR:                                                                              1.0 (3H, s), 1.12 (3H, s), 1.4 (3H, d, J=6Hz), 1.92                           (3H, s), 2.4-3.0 (1H, m), 3.8-4.4 (1H, m), 4.6 (1H,                           d, J=11Hz), 5.23 (1H, d, J=1Hz) δ ppm                        39.        Isomer A - B.p. 110°/0.1 Torr                                      MS: M.sup.+ = 240 (4.7), (100), 117 (85), 123 (76), 41                            (69), 81 (50), 107 (40), 43 (39.5), 93 (36.5), 45                             (36.5), 55 (35), 69 (33)                                                  NMR:                                                                              0.87 (3H, s), 0.95 (3H, s), 1.23 (3H, d, J=6Hz),                              1.81 (3H, s), 2.5-3.9 (2H, m), 4.86 (2H, d, J=2Hz),                           5.53 (1H, m) δ ppm                                                      Isomer B - B.p. 110°/0.1 Torr                                      MS: M.sup.+ = 240 (4.3), 75 (100), 117 (79), 123 (71), 41                         (38), 81 (38), 43 (28), 210 (19), 107 (18.5)                              NMR:                                                                              0.9 (3H, s), 1.0 (3H, s), 1.24 (3H, d, J=6Hz), 1.8                            (3H, m), 2.5-3.7 (2H, m), 4.86 (2H, s), 5.5 (1H, m)                           δ ppm                                                        40.        B.p. 80°/0.1 Torr                                                  MS: M.sup.+ = 194 (31), 104 (100), 43 (51), 121 (43), 122                         (42), 91 (26), 161 (21), 77 (21), 45 (18)                                 NMR:                                                                              1.23 (1.3H, D, J=6Hz), 1.24 (1.7H, d, J=6Hz), 1.7-                            2.3 (2H, m), 3.2-4.4 (2H, m), 4.87 (0.8H, s), 4.93                            (1.2H, s), 7.29 (5H, m) δ ppm                                41.        B.p. 140°/0.01 Torr                                                MS: M.sup.+ =  208 (37), 118 (100), 43 (60), 117 (39), 135                        (37), 136 (35), 105 (35), 91 (34)                                         NMR:                                                                              1.25 (3H, d, J=6Hz), 2.32 (3H, s), 3.3-4.5 (2H, m),                           4.9 (0.7H, s), 4.98 (1.3H, s), 7.22 (4H, m) δ ppm            42.        B.p. 100°/0.001 Torr                                               MS: M.sup.+ = 222 (40), 136 (100), 135 (58), 118 (55), 145                        (38), 91 (34), 163 (31.5), 105 (26), 43 (24)                              NMR:                                                                              1.15 (3H, d, J=6Hz), 1.45 (3H, d, J=6Hz), 2.31 (3H,                           s), 3.7 (1H, m), 4.22 (1H, m), 5.0 (1H, m) δ ppm             43.        B.p. 100°/0.01 Torr                                                MS: M.sup.+  = 224 (50), 134 (100), 135 (98), 121 (94), 136                       (78), 43 (72), 147 (46), 91 (39), 77 (39), 45 (35)                        NMR:                                                                              1.25 (3H, d, J=6Hz), 1.5-2.0 (2H, m), 3.3-4.3 (2H,                            m), 3.77 (3H, s), 4.96 (2H, s), 6.8-7.4 (4H, m) δ ppm        44.        B.p. 110°/0.01 Torr                                                MS: M.sup.+  = 238 (47), 152 (100), 161 (75), 134 (62), 43                        (33), 121 (31), 91 (28), 204 (17), 65 (16), 77 (16)                       NMR:                                                                              1.16 (3H, d, J=6Hz), 1.3-1.6 (3H, m), 3.5-4.0 (1H,                            m), 3.79 (1H, s), 3.8 (2H, s), 4.27 (1H, t), 4.8-5.3                          (1H, m), 6.8-7.6 (4H, m) δ ppm                               45.        B.p. 73°/0.01 Torr                                                 MS: M.sup.+  = 200 (42), 67 (100), 41 (97), 168 (62), 110 (60),                   81 (60), 55 (56), 95 (47), 143 (36)                                       NMR:                                                                              0.9 (3H, t), 1.2-2.1 (13H, m), 3.4 (1H, m), 3.83                              (1H, s), 4.72 (1.6H, s), 4.9 (0.4H, s) δ ppm                 46.        B.p. 66°/0.01 Torr                                                 MS: M.sup.+  = 214 (43), 67 (100), 95 (86), 81 (81), 41 (79),                     101 (58), 60 (57), 168 (43), 114 (40), 55 (38), 87                            (37)                                                                      NMR:                                                                              0.1 (3H, t), 1.43 (3H, d), 3.4 (1H, bm), 3.9 (1H,                             bs), 4.25 (1H, q) δ ppm                                      47.        B.p. 118°/12 Torr                                                  MS: M.sup.+  = 200 (74.3), 185 (19.6), 167 (2.3), 154 (23.7),                     139 (20.5), 137 (19.6), 136 (15.6), 121 (31.8), 112                           (29.1), 111 (28.6), 110 (22.3), 109 (33.2), 95 (59.1),                        81 (77.3), 75 (100), 74 (59.5), 69 (73.6), 67 (32.7),                         59 (29.5), 55 (55.9), 53 (21.8), 43 (30.0), 41 (89.8)                     NMR:                                                                              0.70-1.08 (5H, m), 1.10-1.32 (4H, s), 1.40-2.15 (8H,                          m), 3.83-4.05 (1H, m), 4.60-5.17 (2H, q) δ ppm               48.        B.p. 113°/13 Torr                                                  MS: M.sup.+  = 214 (59.4), 199 (48.9), 170 (52.8), 155 (24.4),                    137 (81.1), 128 (43.3), 127 (41.67), 117 (26.7), 109                          (20.6), 95 (100), 81 (99.3), 75 (89.4), 74 (62.8),                            69 (55.0), 67 (40.0), 59 (40.6), 55 (62.2), 41 (98.9)                     NMR:                                                                              0.75-1.25 (12H, m), 1.40-2.10 (8H, m), 3.86-4.08                              (1H, m), 4.80-5.18 (1H, q) δ ppm                             49.        B.p. 110°/13 Torr                                                  MS: M.sup.+  = 228 (10.7), 199 (67.6), 170 (7.1), 155 (6.9),                      137 (100), 128 (14.8), 127 (15.3), 121 (14.3), 109                            (9.3), 95 (54.9), 81 (62.6), 75 (31.9), 74 (26.6),                            69 (26.9), 67 (23.1), 59 (15.4), 55 (34.6), 41 (59.9)                     NMR:                                                                              0.7-1.20 (12H, m), 1.50-2.10 (10H, m), 3.85-4.05 (1H,                         m), 4.70-4.85 (1H, t) δ ppm                                  50.        B.p. 56°/0.15 Torr                                                 MS: M.sup.+  = 242 (7.4), 199 (67.3), 170 (6.9), 155 (6.5),                       152 (4.1), 137 (100), 128 (13.8), 127 (14.3), 121                             (9.2), 109 (8.8), 95 (44.2), 81 (53.5), 75 (27.6),                            74 (19.8), 69 (22.1), 67 (19.4), 59 (12.4), 55 (34.1)                         43 (18.0), 41 (43.8)                                                      NMR:                                                                              0.70-1.25 (12H, m), 1.39-2.15 (12H, m), 3.85-4.05                             (1H, m), 4.75-5.05 (1H, t) δ ppm                             51.        B.p. 146°/14 Torr                                                  MS: M.sup.+  = 256 (0.9), 241 (6.5), 213 (43.3), 170 (36.8),                      155 (9.5), 137 (83.6), 128 (23.9), 127 (23.6), 109                            (19.9), 95 (88.6), 81 (82.1), 75 (32.8), 74 (26.9),                           69 (34.3), 67 (44.8), 59 (18.9), 55 (44.8), 53                                (20.9), 43 (100), 41 (76.1)                                               NMR:                                                                              0.75-1.24 (12H, m), 1.40-2.05 (15H, m), 4.12-4.30                             (1H, m) δ ppm                                                52.    MS: M.sup.+  =  120 (<1); m/e: 90 (76), 73 (17), 42 (29), 41                      (100)                                                                     NMR:                                                                              1.45-3.55 (4H, bm), 3.83 (2H, t), 4.42 (1H, d, d),                            4.80 (1H, d, d) δ ppm                                               IR: 2960, 2910, 2850, 2730, 1095, 1050, 830 cm.sup.-1                  53.    MS: M.sup.+  = 134 (<1); m/e: 90 (86), 73 (22), 45 (24), 43                       (37), 41 (100)                                                            IR: 2950, 2910, 2860, 2725, 1110, 1045, 865 cm.sup.-1                  54.    MS: M.sup.+  = 148 (7); m/e: 130 (26), 90 (100), 73 (29), 61                      (44), 59 (46), 43 (94), 41 (86)                                           IR: 2980, 2925, 2870, 2720, 1080, 1060, 1040, 855 cm.sup.-1            55.    MS: M.sup.+  = 162 (<1); m/e: 132 (53), 89 (46), 83 (38), 77                      (24), 55 (100), 41 (47)                                                   IR: 2950, 2925, 2870, 2725, 1105, 1045, 860 cm.sup.-1                  56.        vide p. 31 of this specification                                   57.    MS: M.sup.+  = 232 (0); m/e: 145 (100), 87 (18), 83 (42), 67                      (17), 55 (69), 45 (18), 43 (23), 41 (53)                           __________________________________________________________________________

Depending upon the nature of the other constituents in compositions towhich they are added, the compounds of formula (I) can develop variousodoriferous or gustative notes such as fruity, green, alliaceous,caramel-like or slightly burnt and rubbery notes.

These organoleptic characteristics render the compounds of formula (I)particularly suitable for the aromatization of beverages such as fruitjuices, syrups, vegetable juices or coffee drinks and soups or for thearomatization of tobacco products.

When the compounds of formula (I) are used as perfuming ingredients,they can develop upon dilution powerful and natural fruity typefragrances.

The term "foodstuff" is used broadly and includes, for example, coffee,tea or chocolate. The term "tobacco" includes natural tobacco andtobacco substitutes, whether of natural or synthetic origin, intendedfor smoking in pipes, cigars or cigarettes, for chewing, or for the useas snuff.

The concentration at which the compounds of formula (I) can be used asflavouring agents, in accordance with the invention, can vary widely,depending upon the specific organoleptic effect it is desired to achieveand the type of material to which they are added. Typically, interestingflavouring effects can be achieved with amounts ranging from 0.01 to 100ppm (parts per million) by weight of the flavoured material.

Preferentially, this concentration is comprised between about 0.01 and10 ppm. The compounds of formula (I) in which m is 1, viz. the oxidederivatives, can be used at concentrations of about 0.1-50 ppm. Theeffects achieved by the use of these oxides is particularly interestingas they enhance the natural character of the fruity note of thematerials to which they are added. Their effect, though, is lessmarkedly characteristic than that achieved by the correspondingoxathianes or oxathiolanes compounds; more specifically, they are lesspowerful than these latters.

When used as perfuming ingredients, the compounds of formula (I) can beused at concentrations which typically are of the order of 0.01% byweight based on the total weight of the perfuming composition in whichthey are incorporated. Preferential concentrations range from about 0.01to 0.1%. The compounds of formula (I) can be used on their own or incompositions containing one or more other flavouring or odoriferouscompounds, in diluted or concentrated solutions in the solventsconventionally employed for flavouring and perfumery, for example ethylalcohol, triacetin, diethylene-glycol and diethyl phthalate.

Among the compounds listed above, the following possess especiallyinteresting organoleptic properties:

2-methyl-4-propyl-1,3-oxathiane,

4-propyl-1,3-oxathiane,

2,2-dimethyl-4-propyl-1,3-oxathiane,

2-ethyl-4-propyl-1,3-oxathiane,

2-pentyl-4-propyl-1,3-oxathiane,

4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-6-methyl-1,3-oxathiane and

5-butyl-2-oxa-4-thiabicyclo[4.3.0.]nonane,

together with their corresponding 3-oxide derivatives, namely the2-methyl-4-propyl-1,3-oxathiane-3-oxide.

The compounds of formula (I), in which m is zero, can be obtained by aprocess which comprises reacting a thiol-alcohol of formula (II)##STR8## (in which symbols R³ to R⁸ and index n have the aforementionedmeaning) with a carbonyl compound of formula (III) ##STR9## (in which R¹and R² have the meaning described above) in the presence of an acidcatalyst.

The sulphur compounds of formula (II), used as starting materials in theprocess described above, can be obtained by a process which consists (a)in reacting hydrogen sulphide and the desired unsaturated carboxylicacid or, if desired, one of its corresponding esters and (b) reducing orhydrolizing, respectively, the sulphur addition compound thus obtained.

The alcohols of formula (II) can also be prepared by reducing thecorresponding aldehydes, e.g. according to the procedure described inGerman Patent Application DOS No. 2,338,680.

In the preparation of the compounds of formula (I), carbonyl derivatives(III) can be replaced by their corresponding ketal or acetalderivatives.

Typically, the compounds of formula (I) were prepared in accordance withthe following method:

A mixture of 1.34 g (10 mM) of 3-mercapto-hexanol, 2.2 g (50 mM) ofacetaldehyde and 20 ml of cyclohexane were refluxed in the presence of afew milligrams of p-toluenesulphonic acid in a reaction vessel equippedwith a water sepator device. The reaction was over in about 30 minutesas indicated by the total recovery of the theoretical amount of waterformed. The residue was successively washed with a 10% aqueous NaHCO₃solution and water. The aqueous phase was extracted with ether (2fractions) and the ethereal layers thus separated were concentrated toyield 1.5 g of a residue which on distillation gave a fraction havingb.p. 82°-5°/10 Torr; n_(D) =1.4790; d₄ ²⁰ =0.9703; IR (neat): 2940,2905, 2804, 2700, 1083, 664 cm⁻¹ ; NMR (CDCl₃ ; 90 MHz): 0.95 (3H); 1.5(3H, d); 1.5 (6H, m); 3.08 (1H, m); 3.58 and 4.20 (2H, m); 4.8 (1H, q) δppm.

The material obtained essentially consisted of a mixture of twostereoisomers, defined as cis and trans, in a weight ratio of about 9:1,respectively. Consequently, 2-methyl-4-propyl-1,3-oxathiane is betterrepresented by the following formula ##STR10## which in turnindifferently defines one or the other of the compounds of formula##STR11##

Moreover, each of the above indicated epimers can occur in a racemicform or in the form of one of its enantiomers. This applies equally wellto all the compounds of formula (I).

These isomers could be separated by means of vapour phase chromatographyby using a 20 M CARBOWAX column. The compounds obtained werecharacterized by the following physical data:

Isomer A

MS: M⁺ =160 (64.5); M+2⁺ (2.5); m/e: 145 (67.5); 116 (13); 101 (51); 87(82.5); 73 (71.5); 60 (58); 55 (100); 45 (72); 41 (72); 41 (66.5).

Isomer B

MS: M⁺ =160 (62); M+2⁺ (2.5); m/e: 145 (65); 116 (12.5); 101 (48); 87(78.5); 73 (75); 60 (62.5); 55 (100); 45 (78); 41 (62).

For all practical purposes and in accordance with the invention, themixture obtained in accordance with the above described method cansatisfactorily be employed. However, especially for their use inperfumery, the two isomers can be separated and individually used forperfume compounding, the cis isomer being preferred.

3-Mercapto-hexanol, used as starting material in the above describedprocess, can be synthetized according to the procedure described inHouben-Weyl, Methoden der Organischen Chemie 9, 21 (1955), or in ActaChem. Scand. 25, 1908 (1971). This alcohol had the following analyticaldata: B.p. 45°/0.001 Torr; n_(D) =1.4796; d₄ ²⁰ =0.9744.

Typically, said alcohol could be prepared as follows:

(a) 8.36 g (0.11 M) of thio-acetic acid were added dropwise to 9.8 g(0.1 M) of hex-1-en-3-one while the reaction temperature increased to50°. After 1 h stirring at that temperature, 3-oxohexyl thioacetate wasrecovered at b.p. 111°-3°/10 Torr.

(b) 15.6 g (0.09 M) of the said thioacetate in 50 ml of anhydrous etherwas added slowly to a suspension of 3.8 g (0.1 M) of LiAlH₄ in 100 mlether in a nitrogen atmosphere. Once the addition is over, the reactionmixture was refluxed during 1 h, then it was cooled to 0° and the excessof LiAlH₄ was decomposed by slow addition of 10 ml of water followed by200 ml of 10% HCl. After separation, the ethereal phase was washed withwater, dried over MgSO₄ and concentrated. A distillation over a Vigreuxcolumn afforded the desired thio-alcohol in 85% yield.

Alternatively, the alcohols of formula (II) can be synthesized byreacting an α,β-unsaturated ketone with thio-acetic acid as follows:

(a') 0.11 M of thio-acetic acid were added dropwise to 0.1 M of theα,β-unsaturated ketone of formula ##STR12## The reaction mixture wasthen heated for a time period ranging from about 1 to 6 h at atemperature of about 50°-105.

(b') The reduction of the obtained thio-acetate into its correspondingthio-alcohol was carried out by means of LiAlH₄ as indicated sub letter(b).

The compounds of formula (I) in which index m is 1, can be prepared byoxidizing the oxathianes or oxathiolanes of formula (I), in which m iszero, by conventional techniques. Thus2-methyl-4-propyl-1,3-oxathiane-3-oxide, e.g., was prepared by oxidizing2-methyl-4-propyl-1,3-oxathiane by means of H₂ O₂ according to theprocedure described in J. Am. Chem. Soc. 90, 309 (1968) or by means ofperbenzoic acid, m-chloro-perbenzoic acid--vide: Houben-Weyl, IX, GeorgThieme Verlag, 213 (1955)--, or m-periodic acid--vide: J. Org. Chem. 27,282 (1962).

Typically, 2-methyl-4-propyl-1,3-oxathiane-3-oxide could be prepared asfollows:

40 mMoles of 2-methyl-4-propyl-1,3-oxathiane were dissolved in 20 ml ofCH₂ Cl₂ and to this solution there were added 38 mMoles ofm-chloro-perbenzoic acid (80%) in 60 ml of CH₂ Cl₂, and the reactionmixture was stirred at 0° during 1 h. The formed acid was precipitatedby the addition of gaseous NH₃. After filtration, and evaporation of thevolatile fractions, the crude material was fractional distilled undervacuum, and the distillate subjected to separation by columnchromatography on SiO₂ (Merck 60; C), eluant: CHCl₃.

The isolated compound had the following physical data:

electronic ionization: m/e: 132 (41.8); 89 (42.5); 83 (41.4); 77 (23.1);55 (100); 43 (16.7); 41 (38.6); 29 (19.2); 27 (18.4);

chemical ionization: (M+1)⁺ =177 (23); m/e: 161 (28); 145 (17); 133(100); 117 (99); 115 (46.5); 99 (14.5); 83 (50.5);

IR: 2710, 1035 cm⁻¹ ;

NMR: (90 MHz; CDCl₃): 0.97 (3H, t); 1.68 (3H, d); 1.1 to 2.2 (6H, m);2.67 (1H, broad band m); 3.62 (1H, m); 4.02 (1H, m); 4.1 (1H, q) δ ppm.

Owing to the presence of an oxygen atom bonded to the cyclanic sulphurand the simultaneous presence of chirality centres in positions 2 and 4of the ring, 2-methyl-4-propyl-1,3-oxathiane-3-oxide can occur not onlyin the form of a cis or trans cyclanic isomer relative to thesubstituents on the ring, but also as an axial or an equatorial isomerwith regard to its sulphoxide bond.

The separation of these four isomers could be achieved as indicatedabove by careful fractional distillation followed by columnchromatography on silica gel(eluant: CHCl₃). The isolated compoundsshowed the following analytical characteristics:

cis-equatorial

MS: M⁺ =160 (<1); m/e: 132 (52), 89 (52), 83 (40), 77 (23), 55 (100), 43(68), 41 (53), 29 (65).

IR (neat): 2960, 2920, 2860, 1460, 1100 cm⁻¹ ;

cis-axial

MS: M⁺ =160 (<1); m/e: 132 (64), 89 (62), 83 (49), 77 (28), 55 (100), 41(46).

IR (KBr): 2950, 2850, 1450, 1100 cm⁻¹ ;

trans-equatorial

MS: M⁺ =160 (<1); m/e: 132 (61), 89 (58), 83 (45), 77 (39), 55 (100), 41(51).

IR (neat): 2960, 2920, 2860, 1460, 1100, 1050 cm⁻¹

trans-axial

MS: M⁺ =160 (<1); m/e: 132 (25), 89 (25), 83 (34), 55 (100), 43 (38), 41(53).

IR (neat): 2960, 2920, 2860, 1450, 1100, 1040 cm⁻¹.

The above described processes have been used for the preparation of thecompounds listed in the Table. The temperatures are indicated in degreescentigrade and the abbreviations have the meaning common in the art.

The invention is illustrated by the following Examples.

EXAMPLE 1 Aromatization of foodstuffs

A. Two syrups of raspberries and black-currants type, respectively, wereprepared by diluting 1 part by weight of commercial syrup with 4 and 9parts by weight, respectively, of water. The beverages thus obtainedwere flavoured with a proportion of 0.50 ppm and 0.10 ppm, respectively,of 2-methyl-4-propyl-1,3-oxathiane.

The flavoured beverages were subjected to organoleptic evaluation by apanel of experienced tasters whose judgment was expressed as follows:

the flavoured raspberry syrup possessed an improved top note and anoverall aroma which was fuller and fresher than that of the unflavouredsyrup,

the flavoured black-currant syrup showed a fuller and a more naturaltaste than the unflavoured one. It possessed moreover a better definedgreen and woody note.

B. A commercially available tomato juice possessing a bland taste wasflavoured with 2-methyl-4-propyl-1,3-oxathiane by using it at aconcentration of 0.10 ppm based on the total weight of the flavouredfoodstuff. The tomato juice thus aromatized presented a more natural topnote when compared to the unflavoured material. It possessed as well afresher and more fruity character than this latter.

C. A coffee drink was prepared by dissolving 1 g of commercialspray-dried coffee in boiling water. The beverage was then flavoured byadding to it at a concentration of 0.025 ppm, based on the weight of theflavoured material, 2-methyl-4-propyl-1,3-oxathiane. The thus flavouredbeverage possessed a fuller taste of coffee and showed a more markedpleasant smoky-woody character.

D. 100 g of "American blend" tobacco were sprayed with 2 g of a 0.01%solution of 2-methyl-4-propyl-1,3-oxathiane in 95% ethanol, and thetobacco thus flavoured was used to manufacture cigarettes. As a control,cigarettes were also manufactured from the same tobacco sprayed with 95%ethanol alone. The smoke from the cigarettes was subjected toorganoleptic evaluation by a panel of flavour experts, who unanimouslystated that the smoke of the flavoured cigarettes possessed a moremarked "tobacco" character and a more pleasant note as compared with thesmoke of the control cigarettes.

EXAMPLE 2

A base flavouring composition of the "Tutti-Frutti" type was prepared byadmixing the following ingredients (parts by weight):

    ______________________________________                                        Vanillin         50                                                           Amyl butyrate    20                                                           Benzyl acetate   50                                                           Ethyl acetate   100                                                           Orange oil      100                                                           Citral          120                                                           Benzyl alcohol  440                                                           Total           1000                                                          ______________________________________                                    

Two flavour compositions were then prepared by mixing the followingingredients (parts by weight):

    ______________________________________                                                       Flavour A Flavour B                                                           (control) (test)                                               ______________________________________                                        "Tutti-Frutti" base (as                                                       indicated above)   100        100                                             2-Methyl-4-propyl-1,3-oxathiane                                               at 0.1% in 95% ethanol                                                                          --           25                                             95% ethanol        900        875                                                               1000        1000                                            ______________________________________                                    

Flavour compositions A and B were then individually subjected to anevaluation by dissolving them, at a concentration of 0.10% by weight, ina sugar syrup prepared by dissolving 650 g of sucrose in 1000 ml ofwater. The majority of the taste panel members stated that the syrupflavoured with composition B presented an improved top note as well as amore fruity and fuller character as compared with the syrup flavouredwith composition A.

EXAMPLE 3

A. A commercial compote has been flavoured with2-methyl-4-propyl-1,3-oxathiane-3-oxide at a concentration of 5 ppmbased on the weight of the flavoured material. The flavoured foodstuffwas then subjected to an evaluation by a panel of experienced tasterswho stated that its taste was greener and more fruity than that of theunflavoured material. It possessed moreover a character reminiscent ofrhubarb or green berries.

B. A commercial black-currant juice was flavoured with the saidoxathiane-oxide at a concentration of 2 ppm. It was found that thetypical black-currant character was thus enhanced.

C. By proceeding in an analogous way, a rhubarb compote was flavoured byusing the said oxathiane-oxide at a concentration level of 3 ppm. Thecharacteristic note of rhubarb was thus reinforced.

D. A coffee drink was prepared by dissolving 1 g of commercialspray-dried coffee in boiling water. The beverage was then flavoured byadding to it at a concentration of 1 ppm, based on the weight of theflavoured material, 2-methyl-4-propyl-1,3-oxathiane-3-oxide. The thusflavoured beverage possessed a fuller and richer taste of coffee andshowed a slightly fruity character, typical for certain coffeequantities.

E. 100 g of "American blend" tobacco were flavoured as indicated inExample 1 D. by using 2-methyl-4-propyl-1,3-oxathiane-3-oxide at aconcentration level of 10 ppm, based on the total weight of theflavoured tobacco. The smoke of the thus manufactured cigarettes had afuller taste and aroma of tobacco.

EXAMPLE 4

A base flavouring composition of "black-currant" type was prepared byadmixing the following ingredients (parts by weight):

    ______________________________________                                               Vanillin        50                                                            Ethyl maltol    10                                                            α-Ionone 10%*                                                                           10                                                            Amyl acetate    10                                                            Amyl butyrate   20                                                            Eugenol         20                                                            Buchu oil       20                                                            Ethyl butyrate  50                                                            Triacetin       810                                                           Total           1000                                                   ______________________________________                                         *in 95% ethanol                                                          

By using the above base composition, there were prepared two novelflavouring compositions by mixing the following ingredients (parts byweight):

    ______________________________________                                                       Flavour A Flavour B                                                           (control) (test)                                               ______________________________________                                        "Black-currant" base comp-                                                    osition (as indicated above)                                                                     100        100                                             2-Methyl-4-propyl-1,3-oxathiane                                               at 1% in 95% ethanol                                                                            --           20                                             95% ethanol        900        880                                                               1000        1000                                            ______________________________________                                    

The two above compositions A and B were evaluated by tasting them in anacidulated sugar syrup vehicle as indicated in Example 2 at aconcentration of 0.1% by weight. The syrup flavoured with composition Bhas a fresher and more natural flavour character than that flavouredwith composition A. Its taste was analogous to that developed byblack-currant fruits.

EXAMPLE 5

Two base flavouring compositions of "grape-fruit" type were prepared bymixing together the following ingredients (parts by weight):

    ______________________________________                                                        Flavour A Flavour B                                                           (control) (test)                                              ______________________________________                                        Grape-fruit oil    200        200                                             2-Methyl-4-propyl-1,3-oxathiane                                               at 0.1% in 95% ethanol                                                                          --           25                                             95% Ethanol        800        775                                                               1000        1000                                            ______________________________________                                    

The above base compositions were tasted in an acidulated sugar syrupvehicle as indicated in Example 2. The foodstuff flavoured withcomposition B possessed a more marked "grape-fruit" character as well asa more juicy taste.

EXAMPLE 6

A base perfuming composition of "plum" type was prepared by mixingtogether the following ingredients (parts by weight):

    ______________________________________                                        2,6,6-Trimethyl-but-2-en-1-oyl-cyclohex-2-ene                                 at 10%*                   400                                                 1-(3,3-cyclohex-6-en-1-yl)-pent-4-en-1-one                                    at 1%*                    200                                                 Dodecalactone             150                                                 Decalactone               100                                                 Menthyl acetate           100                                                 Dimethyl-benzyl-carbinyl butyrate                                                                        50                                                 Total                     1000                                                ______________________________________                                         *in diethyl phthalate                                                    

By adding to 970 g of the above composition 30 g of a 1% solution of2-methyl-4-propyl-1,3-oxathiane in diethyl phtalate, there was obtaineda novel composition the note of which had a more natural, refreshing andfruity plum character as compared to the base composition.

EXAMPLE 7

A base perfuming composition of "Chypre" type was prepared by mixing thefollowing ingredients (parts by weight):

    ______________________________________                                        Bergamot oil          250                                                     iso-Methylionone      60                                                      Synth. rose oil       60                                                      Synth. Jasmin oil     60                                                      Coumarin              50                                                      Oriental Sandel-wood oil                                                                            50                                                      Ylang oil             40                                                      Musc ketone           40                                                      Bourbon vetyver oil   40                                                      Styrax resinoid 50%*  30                                                      Absolute Oak-moss     30                                                      Dodecanal 1%*         30                                                      Hydroxycitronellal    30                                                      Synth. civet 10%*     30                                                      Labdanum resinoid 50%*                                                                              30                                                      Undecenal 10%*        20                                                      Musc ambrette         20                                                      Synth. rose absolute  20                                                      Synth. Jasmin absolute                                                                              20                                                      Patchouli             15                                                      Neroli Bigarade       15                                                      Methyl-nonacetaldehyde 1%*                                                                          15                                                      Eugenol               15                                                      Orris concrete        10                                                      Tarragon              10                                                      Vanillin              10                                                      Total                 1000                                                    ______________________________________                                         *in diethyl phthalate                                                    

By adding to 990 g of the above base composition, 10 g of a 10% solutionof 2-methyl-4-propyl-1,3-oxathiane in diethyl phthalate, there wasobtained a novel composition which possessed an improved diffusivenessand a top note with a more defined fruity character than the basecomposition.

EXAMPLE 8

A. A natural black-currant juice was flavoured by adding to it trans2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at a concentration of5 ppm by weight, based on the weight of the flavoured material. The thusflavoured beverage possessed a more fruity, woody taste which conferreda more natural character as compared to the unflavoured material; theodour of the flavoured beverage was somewhat greener.

B. A natural passion fruit juice was flavoured by adding to it trans2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at a concentration of2.5 ppm. The flavoured beverage possessed as compared to the naturaljuice an enhanced fruity note as well as a more juicy character.

C. A canned natural grape-fruit juice was flavoured by adding to ittrans 2-methyl-4-propyl-1,3-oxathiane-equatorial 3-oxide at aconcentration of 5 ppm. The flavoured beverage possessed as compared tothe natural juice a fresher and more fruit pulp character.

D. An instant onion soup was prepared by dissolving a commercial gradesoup powder into boiling water. The thus prepared foodstuff wasflavoured by adding to it cis 2-methyl-4-propyl-1,3-oxathiane-equatorial3-oxide at a concentration of 1 ppm. The taste of the flavoured soup hadmore body and presented a fresher onion and meaty character as comparedto the unflavoured material.

The Examples given hereinabove shall not be construed to restrict anyhowthe scope of the present invention. By replacing the effectiveingredients indicated therein by another one of the compounds defined byformula (I), namely those listed in the Table, analogous effects wereobserved. In some cases, however, by their use a more defined sulphurytaste developed in the materials to which they are added, thus limitingthe extent of their applications.

What is claimed is:
 1. A perfume composition comprising a small butodoriferously effective amount of (A) a compound of formula (I):##STR13## in which: (a) n stands for 1 and m represents zero or 1, andeach of symbols R¹ to R⁸ represents a hydrogen atom or a saturated orunsaturated, linear or branched alkyl radical containing from 1 to 11carbon atoms, or(b) n stands for 1 and m represents zero or 1, each ofsymbols R¹, R², R³ and R⁴ have the above-described meaning, R⁵ and R⁷each represents hydrogen and R⁶ together with R⁸ and the carbon atomscarrying them, in positions 5 and 6 respectively, form a lower alkylsubstituted or unsubstituted cyclopentane or cyclohexane ring, or (c) nstands for 1 and m represents zero or 1, each of symbols R¹, R³, R⁵, R⁶and R⁷ represents hydrogen, R² represents a lower alkyl radical or ahydrogen atom, R⁴ represents a para-lower alkyl or lower alkoxysubstituted or unsubstituted phenyl or a lower alkyl substituted orunsubstituted cyclohexenyl radical, and R⁸ stands for a lower alkyl, or(d) n stands for 1 and m represents zero or 1, each of symbols R¹, R³,R⁵, R⁶ and R⁷ represents hydrogen, R² represents a para-lower alkyl orlower alkoxy substituted phenyl or a lower alkyl substituted orunsubstituted cyclohexenyl radical, R⁴ represents a lower alkyl radicalor a hydrogen atom, and R⁸ stands for a lower alkyl or a hydrogen;and(B) another oderiferous compound or a perfume base.
 2. A compositionaccording to claim 1, in which said compound of formula (I) is in theform of one of its epimers or enantiomers.
 3. A composition according toclaim 1, in which said compound of formula (I) is in the form of amixture of its epimers or enantiomers.
 4. Method for improving orenhancing the odoriferous properties of perfumes which comprises addingthereto a small but odoriferously effective amount of at least onecompound of formula (I): ##STR14## in which: (a) n stands for 1 and mrepresents zero or 1, and each of symbols R¹ to R⁸ represents a hydrogenatom or a saturated or unsaturated, linear or branched alkyl radicalcontaining from 1 to 11 carbon atoms, or(b) n stands for 1 and mrepresents zero or 1, each of symbols R¹, R², R³ and R⁴ have theabove-described meaning, R⁵ and R⁷ each represents hydrogen and R⁶together with R⁸ and the carbon atoms carrying them, in positions 5 and6 respectively, form a lower alkyl substituted or unsubstitutedcyclopentane or cyclohexane ring, or (c) n stands for 1 and m representszero or 1, each of symbols R¹, R³, R⁵, R⁶ and R⁷ represents hydrogen, R²represents a lower alkyl radical or a hydrogen atom, R⁴ represents apara-lower alkyl or lower alkoxy substituted or unsubstituted phenyl ora lower alkyl substituted or unsubstituted cyclohexenyl radical, and R⁸stands for a lower alkyl, or (d) n stands for 1 and m represents zero or1, each of symbols R¹, R³, R⁵, R⁶ and R⁷ represents hydrogen, R² apara-lower alkyl or lower alkoxy substituted or unsubstituted phenyl ora lower alkyl substituted or unsubstituted cyclohexenyl radical, R⁴represents a lower alkyl radical or a hydrogen atom, and R⁸ stands for alower alkyl or a hydrogen atom.
 5. The method of claim 4 wherein thecompound of formula II is 2-methyl-4-propyl-1,3-oxathiane.
 6. The methodof claim 4 wherein the compound of formula II is2-methyl-4-propyl-1,3-oxathiane-3-oxide.
 7. The method of claim 4wherein the compound of formula II is4-(2,2,6-Trimethyl-cyclohex-5-en-1-yl)-6-methyl-1,3-oxathiane.
 8. Themethod of claim 4 wherein the compound of formula II is5-butyl-2-oxa-4-thiabicyclo[4.3.0]nonane.
 9. The method of claim 4wherein the compound of formula II is2,6-dimethyl-4-(2,2,6-trimethyl-cyclohex-5-en-1-yl)-1,3-oxathiane.
 10. Aperfume composition comprising an odiferously effective amount of offormula (II): ##STR15## wherein each of the symbols R¹ to R⁸ representsa hydrogen atom or a saturated or unsaturated, linear or branched alkylradical, and each of the indexes m and n means 0 or 1; and (B) anotherodoriferous compound or a perfume base.
 11. A perfume composition ofclaim 10 wherein the compound of formula (II) is2-methyl-4-propyl-1,3-oxathiane.
 12. A method for improving or enhancingthe odoriferous properties of perfumes and perfume bases which comprisesadding thereto a small but odoriferously effective amount of at leastone compound of the formula (II): ##STR16## wherein each of the symbolsR¹ to R⁸ represents a hydrogen atom or a saturated or unsaturated,linear or branched lower alkyl radical, and each of the indexes m and nmeans 0 or
 1. 13. A method according to claim 12 wherein the compound offormula (II) is 2-methyl-4-propyl-1,3-oxathiane.
 14. Substantially pure2-methyl-4-propyl-1,3-oxathiane.
 15. 4-Propyl-1,3-oxathiane. 16.2,2-Dimethyl-4-propyl-1,3-oxathiane.
 17. 2-Ethyl-4-propyl-1,3-oxathiane.18. 4-(2,2,6-Trimethyl-cyclohex-5-en-1-yl)-6-methyl-1,3-oxathiane. 19.5-Butyl-2-oxa-4-thiabicyclo[4.3.0]nonane. 20.2,2,-diethyl-4-n-propyl-1,3-oxathiane.
 21. 2,4-dimethyl-1,3-oxathiolane.22. Substantially pure 2-methyl-4-propyl-1,3-oxathiane-3-oxide.
 23. Acompound selected from the group consistingof:4,4,6-trimethyl-1,3-oxathiane, 2,4,4,6-tetramethyl-1,3-oxathiane,2-ethyl-4,4,6-trimethyl-1,3-oxathiane,2-propyl-4,4,6-trimethyl-1,3-oxathiane, 4-propyl-1,3-oxathiane,2-methyl-4-propyl-1,3-oxathiane, 2,2-dimethyl-4-propyl-1,3-oxathiane,2-methyl-2-ethyl-4-propyl-1,3-oxathiane,2-methyl-2,4-dipropyl-1,3-oxathiane, 2-ethyl-4-propyl-1,3-oxathiane,2-ter-butyl-4-propyl-1,3-oxathiane, 2-pentyl-4-propyl-1,3-oxathiane,2-(pent-1-enyl)-4-propyl-1,3-oxathiane,2-methyl-2-hexyl-4-propyl-1,3-oxathiane, 2-octyl-4-propyl-1,3-oxathiane,2-undecyl-4-propyl-1,3-oxathiane, 2-methyl-4-heptyl-1,3-oxathiane,2,2-dimethyl-4-heptyl-1,3-oxathiane, 2-ethyl-4-heptyl-1,3-oxathiane,2-pentyl-4-heptyl-1,3-oxathiane,5-butyl-2-oxa-4-thiabicyclo[4.3.0]nonane,3-methyl-5-butyl-2-oxa-4-thiabicyclo[4.3.0]nonane,5,5,9-trimethyl-2-oxa-4-thiabicyclo[4.4.0]decane,2,5,5,9-tetramethyl-2-oxa-4-thiabicyclo[4.4.0]decane,5,5,9-trimethyl-3-ethyl-2-oxa-4-thiabicyclo[4.4.0]decane,5,5,9-trimethyl-3-propyl-2-oxa-4-thiabicyclo[4.4.0]decane,3,5,5,9-tetramethyl-3-propyl-2-oxa-4-thiabicyclo[4.4.0]decane,2-methyl-4-propyl-1,3-oxathiane-3-oxide, 2-methyl-1,3-oxathiane-3-oxide,2,2-dimethyl-1,3-oxathiane-3-oxide, 4-propyl-1,3-oxathiane-3-oxide,2-pentyl-4-propyl-1,3-oxathiane-3-oxide,2-methyl-6-propyl-1,3-oxathiane,2,4,4,6-tetramethyl-2-propyl-1,3-oxathiane,